Metallized acid polyazo dyes



least one of the radicals R and R3 has a solu-' Patented Oct. 21, 1941 7UNITED/STATES PATENT-TOFFEE v Qa zsa'zss METALLIZED Aom rotmzonrns MosesLfcr'o'ssl y 'Plainfield, and Lincoln M.- Shafer, Upper Montclair, N.J.; assignors to American Cyanamid Company, New York, N. Yr, acorporation of Maine No'Drawing, Application October 31, 1939, y Se1 -ial.No.302,133

1 13' Claims: (01. 260145) This invention relates to ;metalliz,edpolyazo both R d R2 ontain yd o y carbOXyl dyes which show excellentfastness to light and groups ortho to t azo p more particularly,polyazo; dyes metallized with The present invention is not limited to aparth metals of t fifthahdlsixth.gmupsof the ticular process ofproducing the dyes; Normally periodic table of elements especiallyvanadium, 5 y Will e P pa d by coupl t d y o chrgmium tungstenmolybdenum andjtehufium compound with a diazo compound and a diazoazoThis application is in part a continua fi n v f compound. Of course, thepolyazo dyes may be our co-pending application, Serial;No. 150,540,produced by successive couplings of diazoamino filed June 26, 1937,which matured into U. s. compounds which are then rediazotized andPatent No. 2,213,647 on September 3, 1940; further c upled? e end compoents m y be The metallized dyes of the present invention the Samedifferentare obtai d b metallizjng p a dye hav ing Metallization iseffected in the normal mana middle component which is a aihydroxy arylner, for example, by refluxing an aqueous solucompound capable ofcombining with twomoleo 01 t dye h's suitable cules of diazo compoundsin positions ortho to so t g o or mixed metalsthe hydroxy groups, atleast one of the diazo generalf-the new dyes are, k colored compoundshaving a metallizable group such as PQWQ T which argqvite Solublein-lwater and a hydroxyl r ca'rboxyl group ortho to the azo arecapableof producing valuable colors of varied group and at least one endcomponent containing toneswhen d' o i bath 1 W001, silk, 2. solubilizinggroup. The dyes may be repreleather. a '5 goodto sented by the followinggeneral structural forcellent"fastness to light Washing, filling acid,

um; alkalies and sea water. 'The degree of iastness X will vary with theparticular dyes and with the metals used. r R N=N R1(QH)FN=N*RZN=NRK"When dyes of the class here described are metallized with chromiumextraordinary fastness'to light is obtained; Excellent fastness to lightis obtained'when metallization is accomplished with vanadium; tungsten,and tellurium.

Combinations of two'or'mo're of these metals also give excellent resultsand combinations may be made of one or-more'metals belonging to othergroups of the periodic system.

bmzing group v I r I The invention will be described in detail in Incarrying out the present invention the the iouowmg ex-a'mplfi bu-tlt beunderpolyazo dyes are metallized-with one or more stooc-l fi Invent-finIs not hmlted to'the metals of the fifth and sixth groups of the peri-'detafls h i m set for odic table of elements such as vanadium, chro- Exp e 1 n mium, tungsten, molybdenum and tellurium or combinations withother metals such as chromid g gi' tf g gi fi g lgifiifi f gfi gfig inwhich R, R1, R2 and Rsare aryl radicals; the two hydroxyl groups on R1are ortho to'the azo groups, X represents groups such as halogen, alkyl,alkoxy, nitro, carboxyl, sulfonic, hydroxyl and hydrogen. At leastone ofthe radicalsR and Rzvhas a metalliza'ble group ortho to the azo groupconnecting the radical to R1 andat um'copper copper'vanadimni etcuThesBhydrochloric acid (real) and 3.66 parts of sodium binations of metalsreact with the dye to'pr'oduce nitrite keeping the temperature between25 and a product which is not-identicalwith the mixture 0 C The excessof ty is neutralized t of the p s Obtained by treating P F Q V asaturated solution of bicarbonate of soda This e ye w th sepa atemetals. The metallic diazo solution is then added to a solutionconcombination or complex enters into thedye moletaining 5.88 parts ofresorcinol in 200 parts of cule in some manner which is diiferent fromthe water and 8.5 parts bicarbonate of soda. The reaction of a singlemetal. The precise form of mixture is stirred until coupling is completeand chemical combination has not yet been deter- Parts f Soda ash fi h ndiazo sol mined. l tion obtained by treating 14.7 parts of amino azo Theratio oithe metal or m'etei complex to the benzene sulfonio acid in 170parts of water with dye may varywithm wi li t a i 1 3.66 parts ofnitrite and 5.6 parts of acid at pend on th atur o t metal t e number-63" C. is added and the mixture stirred until and nature of themetallizable groups in the dye 515 pl g i o pl t The y i s l ed o withmolecule, Whe rmore than one metaI is to sodium chloride/after thesolution iS made slightcnter the] molecule of the dye, it is, of course,1y acid to Con ohe r s l i ye p ste is necessary that there be aplurality of pairs of dissolved in 800 parts of hotwater and 12 partsmetallizable groups. Such cases correspond to A of sodium acetate added;The solution is heated a species under the general formula in which 601:0 .601 C, and a solution-containing 12 parts of to metallization,

OgN :N '4

N02 7 1 I=N Ill SOSNB Example 2 160 parts of 1-5 dihydroxy naphthaleneis suspended in 2500 parts of water and 400 parts of soda ash is added.The solution is cooled with ice to 5-10 C. and then mixed with the diazoproduct obtained a from 189 parts of 2 amino phenol 4 sulfonic acid. Themixture is stirred until coupling is complete. Then the diazo compoundobtained from 307 parts of the dye produced by coupling para aminosalicylic acid with alpha naphthyl-amine in acid solution is added.Suflicient sodium carbonate to have the reaction alkaline throughout thecoupling is added. Then the mixture is stirred until the second couplingis complete. The reaction must be alkaline throughout the coupling. Themixture is then made acid to Congo and the dye salted out with sodiumchloride. The dye, is filtered and the paste suspended in 6000 parts ofwater and treated with 300 parts of a soluble tungstate, then themixture is boiled for several hours. 4 The resulting dye is then saltedout with sodium ch10: c. ride. It is soluble in water and dyes animalfibers black. Other metals mentioned inthe specification may besubstituted for tungstate and similar metallized products obtained.

The formula for the dye prior to metallization is as Iollows:

160 p rts of isdihydroxynaphthaeseima 16 7 pended in 2500 parts of waterand 400 parts of soda ash is added. The solution is cooled with ice to5-l0 C. and then mixed with the diazo solution from 154 parts of 4 nitro2 amino 1 phenol. The mixture is stirred until coupling is 'complete.Then the diazo solution obtained by diazotizing the 473 parts of thedye, obtained by coupling 2 amino 5 naphthol 7 sulfonic acid withl-TCleves acid is added and suificient soda ash added to keep thecoupling mixture alkaline throughout the coupling. The mixture isstirred until coupling is complete. The reaction mass is then madeslightly acid to Congo and salted out 'OH OH SOaH 11 Example 4 Dissolveone. molecular weight of the dye obtained by coupling 1-5 dihydroxynaphthalene on one side with diazo para cresol' sulfonic acid and .onthe' other with 1 dinaphthyl 5 hydroxy 6 azo naphthyl 8 hydroxy 3-6disulfonic acid in 12-15times its weight in water. Addtwo molecularequivalents of sodium acetate and one molecular equivalent of chromiumchloride and one molecular equivalent of copper sulfate. Adjust the' pHto 4 and boil for several hours testing samples to ascertain the degreeto which metallization has occurred. Adjust if it is necessarywithfurther quantities of sodium acetate, chromium chloride and coppersulfate. until metallization is. complete. Salt. out the. metallized dyewith sodium chloride and dry the press cake at about C. The product is adark powder, soluble in water and producing blue tones of black. I

The formula for the dye prior to metallization is as follows:

' NaOa QE'ivampleid;

Dissolve in, water one molecular equivalent of the dye'obtainedby'coupling to one mole '01? resorcinol first-one mole of amino azoben'zene para sulfonic acid and then one-mole of picramic acid. I.

One molecular equivalent of the above azo dye is dissolved in 4000 partsoftwater. This is made slightly acid to Congo red and then 300 parts of20% sodium acetate added. This solution is heated to 90 C. and asolution of basic chromium acetate made by dissolving 255 parts of basicchromium acetate in 1000 parts fwtdddltth 'il 4' o er a e 18 en ed M 3\is filtered without the addition of Salt.

. One molecular equivalent of the above azo dye is dissolved in 4000parts of water.

hours and 10 parts of sodium chloride per 100 parts by volume is added,made slightly acid to Congo red and filtered. The dye when dry is a darkpowder which dyes wool a yellowish brown tone.,.-' g The formula for thedye prior to is as follows:

floss-Om Ownsmetallization Example 6 154 parts f para nitro ortho aminolphenol are dissolved in 200 parts of water and diazotized with theaddition of 30 parts of 36% hydrochloric acid and 69 parts of sodiumnitrite at 10 C. and cooledto 0 C. r

160 parts of soda ash are added'to the dye produced by coupling 277parts of amino azo benzene para sulfonic acid to 194 parts of hexylresorcinol. The nitro amino phenol diazo is added to this dye andcoupling allowed to stir overnight. The dye is precipitated by additionof 15 parts of sodium chloride per 100 parts of volume and the dye isfiltered. g 1

One molecular equivalent of the above azo dye is dissolved in 4000 partsof water. This is made slightly acid to Congo red and then 300 parts ofExample 7 a The diazo equivalent to 27.7 parts real amin .azo benzenepara sulfonic acid, dissolved; in .500 cc. of solution is coupled to19.4 parts of hexyl resorcinol at 0 to 5 C. in the presence of 20%sodium acetate solution. 2 2.1 parts of sodium picramateare, dissolvedin 400 cc. of

'acidflare added anditheslurry is cooled to 25 C.

At 25-301 Chit isfdiazotized with 6.9 parts'of 'sodiurn.nitritedissolved in water.

After 45 minutes the. diazotization is complete and the thepH isadjusted'to 6. A very faint trace of red shows onfmethyl ;red yellow andit is nega-. tive to brilliant yellow paper. The dye produced This ismade slightly acid to Congo red and then 300 parts of 20% sodium acetateadded. This solution is heated to 90 C. and a solution of basic chromiumacetate made by dissolving 255 parts of basic chromium acetate in 1000parts of water is added. It is then boiled for 3 to 4 hours and 10 partsof sodium chloride per 100 parts by volume is added, made slightly acidto Congo red and. filtered. The dye when dry is a brown powder whichdyes wool a reddish brown tone.

The formula for the dye prior to metallization is as follows:

. I on 011 EOsSON=N-C N=N N=N N02 N a N02 Example 8 22.1 parts of sodiumpicramate are dissolved in 400 parts of water and stirred to completesolution,.then 1,2.6 parts of hydyrochlorick acid, 100% are iadded. Themixture is cooled to 30 C. and diazotized with the addition of 6.9 partsof sodium nitrite dissolved in water. 34.2 parts of chromotropic acidare dissolved in 400 parts of water with the addition of 9.4 parts ofsodium bicarbonate. This solution is added to the picramic acid diazoand allowed to cool over night. The diazo from 27.7 parts of amino azobenzene is added to this monazo dye. 8 parts of magnesium oxide areadded and the coupling is stirred for 4 or-5, hours. 600 parts of saltare added and hydrochloric acid is added until there is a faint butpermanent test on Congo red paper. The dye is filtered after it has beenstirred for several hours to complete precipitation.

One, molecular equivalent of the above azo dye is dissolved in 4000parts of water. This is made slightly acid to Congo red and then 300parts of 20% sodium acetate added. This soluis as follows:

I Examplev9 J j l Dissolve one molecular weight tr the dye'obtained bycoupling 1-5 dihydroxy naphthalene with 2 diazo 1 naphthol 4 sulfonic.acid on one side and with diazo phenylazo nitro phenol azo urea 'J-acidon the other side in ten times its weight of water. Add two molecularequivalents of sodium acetate and two molecular equivalents of chromiumchloride. Adjust the solution to a pH of 3-4 and boil for .4 hours.Salt-out the dye The following table illustrates further dyes which canbe produced according to the present invention.

' Tdble of types of dyes Color produced by p metallized product Firstcomponent Middle component Second component Cr V OH OH NH: Black...Blulsh N V 1 7 black.

NH: I

c1 N=N 0H i HO: SOaH OH x H NH1 V i I i ...d0- Do. on: NHa @5031: .l NO:N'=N I SOaH OH OH Dark Brown.

brown.

OzN NH: A

NH: Dark Dark green. green.

c o no N=N(|f -(|3CH:

HO C\ o=H .M M, Tq of W 1 1- -9 th I V a H Co lor broducd by vmetallized product "First component Middle comppnept Second component; v

Cr V

N=NC-O-CH D a rk 356m.

A brown. HQ- I SOSH N v 1M H: N=NO-CCH: HgN' ..-do. 0 l i v e H0 (LI) 5brown.

B1 k l B h 1 ac uis 0H NH: 5 -"'='b1a'c1;.' N=N 1 5 3* -smH HOzS CH: OH

N=N NHCOHI v110:3 '011 Bluish Black. black. I 7 NH:

HOaS

OH OH NH: OH Reddish Bl nish blue. red.

Hz 0H OH OH NH: OH Blackish Blackish blue. blue.

OH 0H 1 Blue Reddi sh NH: blue.

HOaS

HI E

31 v NH: g I OH V Dark Dark OzN NH: brown. brown.

Middle cigmpiaiiefif Second component Color produced by zpetallizedproduct SOaH Bluish black.

' Brown Bluish black.

Reddish blue.

Bluish black.

Dark

brown.

Dark

blue.

Bluishl red.

3: -arable of types of dye's'Continued' Color produced By 7 metallizedproduct First component. Middle component Second component H 1 OH NH:Black.-- Black.

oiN- NH:

on: H N=N on Hms- S0111 NH: -B1uish Brown.

. red.

".fcnao H OH 0H NH; Black.-- Black t f H i l H N=N f a The unmetallizeddye compounds described in I in which R, R1, R2 and R3 are arylradicals, the hydroxyl groups on R1 are ortho to the azo groups and Xrepresents a member of the group consisting of halogen, alkyl, alkoxy,nitro, carboxyl, sulfonic, hydroxyl and hydrogen, at least one of theradicals R and R2 has a metallizable group ortho to the azo groupconnecting the radical to R1 and at least one of the radicals R and R3has a solubilizing group, and the dye being metallized with at least oneof the metals included in the fifth and sixth groups of the periodictable of elements.

2. Metallized azo dyes, the azo dye component of which has the followingformula:

in which R1 is a radical of the benzene series having the hydroxylgroups ortho to the azo groups and R, R2 and R3 are aryl radicals, atleast one of the radicals R and R2 has a metallizable group ortho to theazo group connecting the radical with the resorcinol radical and atleast one of the radicals R and R3 has a solubilizing group, and the dyebeing metallized with at least one of the metals included in the fifthand sixth groups of the periodic table of elements.

3. Metallized azo dyes, the azo dye component of which has the followingformula:

in which the radicals R, R2 and R3 are aryl radica1s, R1 is a radical ofthe naphthalene series having the hydroxyl groups ortho to the two azogroups, at least one of the radicals R and R2 having a metallizablegroup ortho to the azo group connecting the radical R1, and at least oneof the radicals R and R3 containing a .solubilizing group, and the dyebeing metallized with at least one of the metals included in the fifthand sixth groups of the periodic table of elements.

4. A metallized azo dye according to claim 1 in which both R and R2contain metallizable groups ortho to the azo groups connecting theseradicals with R1.

5. A metallized azo dye according to claim 1 in which Rs' is anaryl-azo-aryl radical.

'6. A metallized azo dye according to claim 1 in which R3 is an arylradical free from an groups except the one connecting to R2.

7. A metallized azo dye according to claim 2 in which R is phenol withthe hydroxyl group ortho to the azo group and R2 is an azobenzeneradical.

8. A metallized azo dye accordihgioeclaim 2 11. The complex chromiumcompound 01. the in which R is: azo dye having the followingiormula:

' OH OH NO 5 O zN f 02 N0, 9. A metallized trisazo dye of the 10 wformula: 011;

CH: H i

in which R2 represents a radical of a 4'-sulfonic acid azobenzene, thedye being metallized with at least one metal included in the fifth andsixth groups of the periodic table of elements. I

10. The complex chromium compound of the azo dye having the followingform 12. A metallized azo dye according to claim 1; in which'both R andR2 contain metalliaable groups ortho to the azo groups connectingthese20 radicals to R1 and the dye metallized with'a mix-; ture of at leastone of the metals included in; the fifth and sixth groups of theperiodic table of elements.

13. A complex chromium-copper compound of;

25 the azo dye having the following formula: j

